CN113956558B - High-density polyethylene waterproof coiled material basement membrane, preparation method thereof and high-density polyethylene waterproof coiled material - Google Patents
High-density polyethylene waterproof coiled material basement membrane, preparation method thereof and high-density polyethylene waterproof coiled material Download PDFInfo
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Abstract
The invention provides a high-density polyethylene waterproof roll basement membrane, a preparation method thereof and a high-density polyethylene waterproof roll, belonging to the technical field of building waterproof materials, wherein the high-density polyethylene waterproof roll basement membrane comprises the following raw material components in parts by weight: 100 parts of high density polyethylene, 40-50 parts of polypropylene, 30-39 parts of linear low density polyethylene, 40-53 parts of metallocene catalyzed polyethylene, 27-33 parts of thermoplastic elastomer and 6-9 parts of free radical initiator. The high-density polyethylene waterproof coiled material basement membrane containing the proportion has a cross-linking structure, and provides high elasticity and high extensibility for the whole molecular structure. The elongation of the high-density polyethylene waterproof coiled material prepared from the high-density polyethylene waterproof coiled material basement membrane is improved by more than 70 percent compared with the elongation of the conventional high-molecular waterproof coiled material.
Description
Technical Field
The application relates to the technical field of building waterproof materials, in particular to a high-density polyethylene waterproof roll basement membrane, a preparation method thereof and a high-density polyethylene waterproof roll.
Background
The waterproof coiled material is a flexible building material product which can be curled into a roll shape and is used for building walls, roofs, tunnels, highways, refuse landfills and the like to resist external rainwater and underground water leakage. The waterproof coiled material is used as a leakage-free connection between an engineering foundation and a building, is a first barrier for waterproofing of the whole engineering and plays a vital role in the whole engineering. Common waterproofing membrane has PVC waterproofing membrane, EPDM waterproofing membrane, TPO waterproofing membrane and HDPE waterproofing membrane etc. wherein, HDPE waterproofing membrane is owing to have green, with advantages such as concrete bonding closely and deeply receive waterproof border and favor.
The HDPE waterproof coiled material is generally used in complex construction sites such as mountain tunnels, urban subways and the like, and generally comprises a bottom film, a hot melt adhesive layer and an isolation layer. The basement membrane of the HDPE waterproof coiled material is contacted with building materials such as rigid concrete, and the extensibility of the basement membrane determines the effectiveness and the service life of the HDPE waterproof coiled material. When building materials such as rigid concrete migrate and crack, because HDPE waterproofing membrane basement membrane extensibility is not enough, often can lead to HDPE waterproofing membrane to be destroyed, take place the seepage accident.
Disclosure of Invention
The application provides a high density polyethylene waterproofing membrane basement membrane, its preparation method and high density polyethylene waterproofing membrane, aims at solving the not good problem of high density polyethylene waterproofing membrane basement membrane extensibility.
On the one hand, the embodiment of the application provides a high-density polyethylene waterproof coiled material basement membrane, which comprises the following raw material components in parts by weight: 100 parts by weight of high-density polyethylene; (b) 40 to 50 parts by weight of polypropylene; (c) 30 to 39 parts by weight of linear low density polyethylene; 40-53 parts of metallocene catalyzed polyethylene; (e) 27 to 33 parts by weight of a thermoplastic elastomer; and (f) 6-9 parts by weight of a free radical initiator.
According to an embodiment of one aspect of the application, the high-density polyethylene waterproof roll base film comprises the following raw material components in parts by weight: 100 parts by weight of high-density polyethylene; (b) 40-45 parts by weight of polypropylene; (c) 30-35 parts by weight of linear low density polyethylene; 45-48 parts of metallocene catalyzed polyethylene; 27-30 parts by weight of a thermoplastic elastomer; and (f) 6-8 parts of a free radical initiator.
According to an embodiment of one aspect of the present application, the base film of the high density polyethylene waterproofing membrane further comprises 1 to 2 parts by weight of an oxygen-resistant stabilizer.
According to an embodiment of one aspect of the present application, the base film of the high density polyethylene waterproofing membrane further comprises a pigment filler.
According to an embodiment of one aspect of the application, the high-density polyethylene waterproof coiled material bottom film comprises the following raw material components in parts by weight: 100 parts by weight of high-density polyethylene; (b) 40-45 parts by weight of polypropylene; (c) 30 to 35 parts by weight of linear low density polyethylene; (d) 45-48 parts by weight of metallocene catalyzed polyethylene; (e) 27 to 30 parts by weight of a thermoplastic elastomer; (f) 6-8 parts by weight of a free radical initiator; (g) 1.6-1.8 parts by weight of an antioxidant stabilizer; (h) 6-8 parts of pigment and filler.
According to an embodiment of one aspect of the application, the free radical initiator is one or more of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 2, 4-dichlorobenzoyl peroxide, or dicumyl peroxide.
According to an embodiment of one aspect of the present application, the antioxidant stabilizer is one or more of antioxidant 1010, antioxidant 168, antioxidant B225, or antioxidant 1330.
According to an embodiment of one aspect of the present application, the pigment and filler is one or more of titanium dioxide, talc, calcium carbonate, color masterbatch or barium sulfate.
In another aspect, the present application provides a method for preparing a base film of a high-density polyethylene waterproof roll, comprising the following steps: providing raw material components according to the weight ratio; the raw material components are melt mixed to extrude into a film.
In another aspect, an embodiment of the present application provides a high density polyethylene waterproof roll, which includes the bottom film of the high density polyethylene waterproof roll, a hot melt adhesive layer, and an isolation layer.
Compared with the prior art, the application has at least the following beneficial effects:
(1) The application provides a high density polyethylene waterproofing membrane basement membrane has high extensibility.
In the application, the high-density polyethylene, the linear low-density polyethylene and the metallocene catalytic polyethylene are used as base materials of the high-density polyethylene waterproof coiled material bottom film, and the free radical initiator promotes the thermoplastic elastomer and the polypropylene high-molecular winding chain segment to perform catalytic crosslinking reaction inside the high-molecular chain segment of the base materials to form a chemical crosslinking bond, so that a crosslinking network structure is formed, and high extensibility is provided for the whole molecular structure.
In the embodiment, the elongation of the waterproof coiled material prepared from the high-density polyethylene waterproof coiled material basement membrane is improved by more than 70% compared with that of a conventional high-molecular HDPE waterproof coiled material when the membrane is broken.
(2) The application provides a high density polyethylene waterproofing membrane basement membrane has good puncture resistance.
Metallocene catalysis polyethylene molecular weight distribution is more homogeneous in this application component, is favorable to improving the compactedness of high density polyethylene waterproofing membrane basement membrane product to effectively improve its puncture resistance.
In the embodiment, the puncture resistance of the high-density polyethylene waterproof coiled material prepared from the high-density polyethylene waterproof coiled material basement membrane is improved by more than 6 percent compared with that of the conventional high-molecular high-density polyethylene waterproof coiled material.
Detailed Description
Embodiments of the present application will be described in further detail with reference to examples. The following detailed description of the embodiments is provided to illustrate the principles of the application and is not intended to limit the scope of the application, i.e., the application is not limited to the described embodiments.
In the description of the present application, it is to be noted that, unless otherwise specified, "a plurality" means two or more; the terms "upper," "lower," "left," "right," "inner," "outer," and the like, indicate an orientation or positional relationship that is merely for convenience in describing the application and to simplify the description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the application. Furthermore, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. "vertical" is not strictly vertical but is within the tolerance of the error. "parallel" is not strictly parallel but within the tolerance of the error.
In the description of the present application, it is also to be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; may be directly connected or indirectly connected through an intermediate. The specific meaning of the above terms in the present application can be understood as appropriate by one of ordinary skill in the art.
High density polyethylene waterproof coiled material basement membrane
The embodiment of the first aspect of the application provides a high-density polyethylene waterproofing membrane basement membrane, which comprises the following raw material components in parts by weight: 100 parts by weight of high-density polyethylene; (b) 40 to 50 parts by weight of polypropylene; (c) 30 to 39 parts by weight of linear low density polyethylene; 40-53 parts of metallocene catalyzed polyethylene; (e) 27 to 33 parts by weight of a thermoplastic elastomer; and (f) 6-9 parts by weight of a free radical initiator.
According to the high density polyethylene waterproofing membrane basement membrane of this application embodiment, through the control to the kind and the content of each component for play synergistic interaction effect between each component, thereby give high density polyethylene waterproofing membrane basement membrane and have high extensibility and good puncture resistance concurrently.
According to the embodiment of the invention, the High Density Polyethylene (HDPE) is a white powder or granular product, the use temperature can reach 100 ℃, and the hardness, the tensile strength and the creep property are superior to those of low density polyethylene; the wear resistance, the electrical insulation, the toughness and the cold resistance are good; good chemical stability, acid resistance, alkali resistance and corrosion resistance of various salts. The high-density polyethylene is used as one of the base materials of the high-density polyethylene waterproof roll basement membrane, so that the mechanical property and the processing property of the waterproof roll can be improved, the waterproof roll is not easy to deform, the weather resistance of the waterproof roll can be improved, the service life of the waterproof roll can be prolonged, and the like.
To improve the overall performance of the roll of waterproofing material, the high density polyethylene may be selected, for example, from the following brands and types of products: HDPE-TR144 from Katalr chemical or ME5500 from LG in Korea or 5121B from Mediterranean Shell.
In order to improve the properties of the waterproofing membrane in combination, the high density polyethylene has a density of 0.94 to 0.96g/cm 3 For example, the density is 0.94g/cm 3 、0.95g/cm 3 Or 0.96g/cm 3 The high-density polyethylene under the density can effectively improve the comprehensive mechanical property of the basement membrane of the high-density polyethylene waterproof coiled material.
According to the embodiment of the invention, the linear low density polyethylene is non-toxic, tasteless and odorless milky white particles, has higher softening temperature and melting temperature compared with LDPE (low density polyethylene), has the advantages of high strength, good toughness, high rigidity, good heat resistance and cold resistance, and the like, also has good environmental stress crack resistance, impact strength, tearing strength and the like, and can resist acid, alkali, organic solvents and the like. The linear low-density polyethylene is used as one of base materials of the basement membrane of the high-density polyethylene waterproof coiled material, and can further improve the mechanical property, the weather resistance and the like of the waterproof coiled material.
To improve the overall performance of the waterproofing membrane, the linear low density polyethylene may be selected, for example, from the following brands and types of products: 7042 of Mediterranean Shell or CNU013 of Exxon Mobil or FB9500 of Korean LG.
In some embodiments, the linear low density polyethylene is 30 to 39 parts by weight based on 100 parts by weight of the high density polyethylene. For example, the linear low density polyethylene is 30 parts by weight, 32 parts by weight, 35 parts by weight, 37 parts by weight, or 39 parts by weight. The linear low density polyethylene may also have a mass ranging in any combination of the above values.
According to the embodiment of the invention, compared with the traditional polyethylene, the metallocene catalyzed polyethylene has high mechanical strength and good optical performance. The metallocene catalyzed polyethylene is used as one of the base materials of the basement membrane of the high-density polyethylene waterproof coiled material, and the mechanical property of the waterproof coiled material can be further improved. Particularly, the metallocene catalyzed polyethylene has uniform molecular weight distribution, which is beneficial to improving the compactness of a high-density polyethylene waterproof coiled material basement membrane product, thereby effectively improving the puncture resistance of the high-density polyethylene waterproof coiled material basement membrane product.
To improve the overall performance of the waterproofing membrane, the metallocene catalyzed polyethylene can be selected, for example, from the following brands and types of products: MC4009 in Exxon Mobil or 2703HH in Exxon or SP4020 in Japanese Priman.
To improve the overall performance of the waterproofing membrane, metallocene catalyzed polyethylene is typically present in a density of 0.92 to 0.94g/cm 3 For example, the density is 0.92g/cm 3 、0.93g/cm 3 Or 0.94g/cm 3 . The metallocene catalyzed polyethylene has uniform molecular weight distribution under the density, and the puncture resistance of the basement membrane of the high-density polyethylene waterproof coiled material can be effectively improved.
In some embodiments, the metallocene-catalyzed polyethylene is present in an amount of from 40 to 53 parts by weight, based on 100 parts by weight of the high density polyethylene. For example, the metallocene catalyzed polyethylene is 40 parts by weight, 42 parts by weight, 45 parts by weight, 46 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, or 53 parts by weight. The metallocene-catalyzed polyethylene may also have a mass ranging in any combination of the above values.
According to an embodiment of the invention, the polypropylene is a polymer of propylene obtained by addition polymerization. Polypropylene is a thermoplastic synthetic resin with excellent performance, and is colorless translucent thermoplastic light general-purpose plastic. Has chemical resistance, heat resistance, electric insulation, high-strength mechanical property, good high-wear-resistance processing property and the like. The mechanical property, the processing property and the weather resistance of the high-density polyethylene waterproof coiled material basement membrane can be improved by adding the polypropylene.
To improve the overall performance of the roll of waterproofing material, polypropylene may be selected, for example, from the following brands and types of products: a petrochemical T03 or exxonmobil CNU013 or a petrochemical 5000SH.
In some embodiments, the polypropylene is 40 to 50 parts by weight based on 100 parts by weight of the high density polyethylene. For example, the polypropylene is 40 parts by weight, 42 parts by weight, 45 parts by weight, 46 parts by weight, 48 parts by weight, or 50 parts by weight. The polypropylene may also have a mass ranging between any combination of the above values.
According to the embodiment of the invention, the thermoplastic elastomer has the excellent performances of high elasticity, aging resistance and oil resistance of the traditional cross-linked vulcanized rubber.
In order to improve the performance of the waterproofing membrane, the thermoplastic elastomer can be selected from the following brands and types of products: POE8401 in Dow chemical or POE3020 in Exxon chemical.
In some embodiments, the thermoplastic elastomer is 27 to 33 parts by weight, based on 100 parts by weight of the high density polyethylene. For example, the thermoplastic elastomer is 27 parts by weight, 28 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight, or 33 parts by weight. The mass of the thermoplastic elastomer may also be in any combination of the above values.
According to an embodiment of the present invention, a radical initiator may be used for the crosslinking reaction of the polymer, and the radical initiator may be 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 2, 4-dichlorobenzoyl peroxide, or dicumyl peroxide.
In some embodiments, the free radical initiator is 6 to 9 parts by weight based on 100 parts by weight of the high density polyethylene. For example, the radical initiator is 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight. The mass of the free radical initiator may also range in any combination of the above values.
In the application, all components of the high-density polyethylene waterproof roll basement membrane are matched with each other to play a role in synergy. Specifically, high-density polyethylene, linear low-density polyethylene and metallocene catalyzed polyethylene are used as base materials of the high-density polyethylene waterproof coiled material bottom film, and a free radical initiator promotes a thermoplastic elastomer and a polypropylene high-molecular winding chain segment to perform catalytic crosslinking reaction inside a high-molecular chain segment of the base materials to form a chemical crosslinking bond, so that a crosslinking network structure is formed, and high extensibility is provided for the whole molecular structure.
In some embodiments, the composition of the base film of the high density polyethylene waterproof roll further comprises 1 to 2 parts by weight of an antioxidant stabilizer (based on 100 parts by weight of the high density polyethylene), for example, 1 part by weight or 2 parts by weight.
According to an embodiment of the present invention, the antioxidant stabilizer may be one or more of antioxidant 1010, antioxidant 168, antioxidant B225, and antioxidant 1330 as a process stabilizer.
In some embodiments, the components of the base film of the high-density polyethylene waterproof roll also comprise pigments and fillers, and the pigments and fillers not only can endow the waterproof roll with colors, but also can play a role in filling, so that the cost is reduced.
In some embodiments, the pigment and filler may be one or more of titanium dioxide, talc, calcium carbonate, color masterbatch, or barium sulfate.
According to an embodiment of one aspect of the invention, the high-density polyethylene waterproof coiled material bottom film comprises the following raw material components in parts by weight: 100 parts by weight of high-density polyethylene; (b) 40-45 parts by weight of polypropylene;
(c) 30-35 parts by weight of linear low-density polyethylene; 45-48 parts of metallocene catalyzed polyethylene; 27-30 parts by weight of a thermoplastic elastomer; 6-8 parts of free radical initiator.
According to an embodiment of one aspect of the invention, the high-density polyethylene waterproof coiled material base film comprises the following raw material components in parts by weight: 100 parts by weight of high-density polyethylene; (b) 40-45 parts by weight of polypropylene; (c) 30 to 35 parts by weight of linear low density polyethylene; 45-48 parts of metallocene catalyzed polyethylene; (e) 27 to 30 parts by weight of a thermoplastic elastomer; (f) 6-8 parts by weight of a radical initiator; (g) 1.6-1.8 parts by weight of an antioxidant stabilizer; (h) 6-8 parts of pigment and filler.
The basement membrane of the high-density polyethylene waterproof coiled material is contacted with building materials such as rigid concrete and the like, is a very critical part in the waterproof coiled material, and the extensibility of the basement membrane determines the effectiveness and the service life of the high-density polyethylene waterproof coiled material. The high-density polyethylene waterproof coiled material basement membrane disclosed by the embodiment of the invention has high extensibility and good puncture resistance.
Preparation of high-density polyethylene waterproof coiled material basement membrane
Embodiments of the second aspect of the present invention provide a method for preparing a base film of a high-density polyethylene waterproofing membrane, the preparation method comprising the steps of: providing raw material components according to the weight ratio; the raw material components are melt mixed to be extruded into a film.
It can be understood that, in order to ensure the reaction to be carried out smoothly, the mixing is carried out under stirring, the stirring speed is 20-30 r/min, and the stirring time is 30-40 min; the extrusion temperature of the extrusion film is 200-220 ℃; after the extrusion film forming, the three-roller calendering process is used for cooling and shaping, and the cooling and shaping temperature is 30-50 ℃.
According to the preparation method of the high-density polyethylene waterproof roll basement membrane, the process is simple, and the prepared high-density polyethylene waterproof roll basement membrane is stable in system.
High-density polyethylene waterproof coiled material
The embodiment of the third aspect of the invention provides a high-density polyethylene waterproof coiled material, which comprises the high-density polyethylene waterproof coiled material bottom film, a hot melt adhesive layer and an isolation layer.
According to the high-density polyethylene waterproof roll material provided by the embodiment of the invention, the high-density polyethylene waterproof roll material base film with high extensibility and good puncture resistance is included, so that the high-density polyethylene waterproof roll material can be applied to complex construction places such as mountain tunnels and urban subways, the service life of the product is long, and the waterproof performance is excellent.
Examples
Example 1
The high density polyethylene waterproofing membrane basement membrane that this embodiment provided does not have: 100 parts of high-density polyethylene, 50 parts of polypropylene, 33.3 parts of linear low-density polyethylene, 53.3 parts of metallocene catalyzed polyethylene, 33.3 parts of thermoplastic polyolefin, 6.6 parts of free radical initiator, 1.6 parts of antioxidant stabilizer and 6.6 parts of titanium dioxide color master batch.
The density of the high density polyethylene is 0.94g/cm 3 。
The metallocene catalyzed polyethylene has a density of 0.92g/cm 3 。
The free radical initiator is 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane.
The antioxidant stabilizer is antioxidant 1010.
The raw materials of the components are prepared into the high-density polyethylene waterproof coiled material basement membrane according to the following method:
placing the components in the weight ratio in a low-speed stirring tank, stirring for 30min at a stirring speed of 20r/min and at a stirring and mixing temperature of 60 ℃ to obtain a mixture;
entering a single-screw extruder through a vacuum negative pressure feeding system, plasticizing and melting the mixture by the single-screw extruder, vacuumizing and exhausting the mixture, and then extruding and molding the mixture from a flat plate mold, wherein the extrusion temperature is 220 ℃;
and (3) determining the thickness of the film through a gap between two rollers, and carrying out three-roller calendering cooling by introducing cooling water into the film, wherein the cooling temperature is 50 ℃, so as to obtain the high-extensibility high-density polyethylene waterproof coiled material basement membrane.
Example 2
The high density polyethylene waterproofing membrane's that this embodiment provided component is: 100 parts of high-density polyethylene, 40 parts of polypropylene, 30 parts of linear low-density polyethylene, 40 parts of metallocene catalyzed polyethylene, 30 parts of thermoplastic polyolefin, 8 parts of free radical initiator, 1.6 parts of antioxidant stabilizer and 6 parts of titanium dioxide color master batch.
The density of the high density polyethylene is 0.96g/cm 3 。
The metallocene catalyzed polyethylene had a density of 0.93g/cm 3 。
The free radical initiator is 2, 4-dichlorobenzoyl peroxide.
The antioxidant stabilizer is antioxidant B225.
The raw materials of the components are prepared into the high-density polyethylene waterproof coiled material basement membrane according to the following method:
placing the components in the weight ratio in a low-speed stirring tank, stirring for 30min at a stirring speed of 20r/min and at a stirring and mixing temperature of 60 ℃ to obtain a mixture;
entering a single-screw extruder through a vacuum negative pressure feeding system, plasticizing and melting the mixture by the single-screw extruder, vacuumizing and exhausting the mixture, and then extruding and molding the mixture from a flat plate mold, wherein the extrusion temperature is 200 ℃;
and (3) determining the thickness of the film through a gap between two rollers, and calendering and cooling the film by three rollers through cooling water, wherein the cooling temperature is 30 ℃, so as to obtain the high-density polyethylene waterproof coiled material basement film with high extensibility.
Example 3
The high density polyethylene waterproofing membrane's that this embodiment provided component is: 100 parts of high-density polyethylene, 46.2 parts of polypropylene, 38.5 parts of linear low-density polyethylene, 40 parts of metallocene catalyzed polyethylene, 27.7 parts of thermoplastic polyolefin, 9.2 parts of free radical initiator, 1.8 parts of antioxidant stabilizer and 7.7 parts of titanium dioxide color master batch.
The density of the high density polyethylene is 0.95g/cm 3 。
The metallocene catalyzed polyethylene has a density of 0.94g/cm 3 。
The free radical initiator is dicumyl peroxide.
The antioxidant stabilizer is antioxidant 168.
The raw materials of the components are prepared into the high-density polyethylene waterproof coiled material basement membrane according to the following method:
placing the components in the weight ratio in a low-speed stirring tank, stirring for 30min at a stirring speed of 20r/min and at a stirring and mixing temperature of 60 ℃ to obtain a mixture;
the mixture enters a single-screw extruder through a vacuum negative pressure feeding system, is plasticized and melted by the single-screw extruder, is extruded and molded from a flat plate die after being vacuumized and exhausted, and has the extrusion temperature of 210 ℃;
and (3) determining the thickness of the film through a gap between two rollers, and calendering and cooling the film by three rollers through cooling water, wherein the cooling temperature is 40 ℃, so as to obtain the high-density polyethylene waterproof coiled material basement film with high extensibility.
Comparative example
Comparative example 1
The high-density polyethylene waterproof coiled material bottom film provided by the comparative example comprises the following components: 100 parts of high-density polyethylene, 50 parts of polypropylene, 33.3 parts of linear low-density polyethylene, 53.3 parts of metallocene catalyzed polyethylene, 33.3 parts of thermoplastic polyolefin, 1.6 parts of antioxidant stabilizer and 6.6 parts of titanium dioxide color master batch.
The density of the high density polyethylene is 0.94g/cm 3 。
The metallocene catalyzed polyethylene has a density of 0.92g/cm 3 。
The antioxidant stabilizer is antioxidant 1010.
The method for preparing the base film of the high-density polyethylene waterproofing membrane is the same as that of example 1.
Comparative example 2
The high-density polyethylene waterproof coiled material bottom film provided by the comparative example comprises the following components: 100 parts of high-density polyethylene, 50 parts of polypropylene, 33.3 parts of linear low-density polyethylene, 33.3 parts of thermoplastic polyolefin, 6.6 parts of free radical initiator, 1.6 parts of antioxidant stabilizer and 6.6 parts of titanium dioxide color master batch.
The density of the high density polyethylene is 0.94g/cm 3 。
The free radical initiator was 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane.
The antioxidant stabilizer is antioxidant 1010.
The method for preparing the base film of the high-density polyethylene waterproofing membrane is the same as that of example 1.
Comparative example 3
The comparative example provides a conventional high-density polyethylene waterproof coiled material basement membrane, which comprises the following components: 100 parts of high-density polyethylene, 33.3 parts of linear low-density polyethylene, 1.6 parts of antioxidant stabilizer and 6.6 parts of titanium dioxide color master batch.
The density of the high density polyethylene is 0.94g/cm 3 。
The antioxidant stabilizer is antioxidant 1010.
The method for preparing the base film of the high-density polyethylene waterproofing membrane is the same as that of example 1.
Comparative example 4
The high-density polyethylene waterproof coiled material bottom film provided by the comparative example comprises the following components: 100 parts of high-density polyethylene, 50 parts of polypropylene, 33.3 parts of linear low-density polyethylene, 53.3 parts of metallocene catalyzed polyethylene, 33.3 parts of thermoplastic polyolefin, 4 parts of free radical initiator, 1.6 parts of antioxidant stabilizer and 6.6 parts of titanium dioxide color master batch.
The density of the high density polyethylene is 0.94g/cm 3 。
The free radical initiator was 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane.
The antioxidant stabilizer is antioxidant 1010.
The method for preparing the base film of the high-density polyethylene waterproofing membrane is the same as that of example 1.
Comparative example 5
The high-density polyethylene waterproof coiled material bottom film provided by the comparative example comprises the following components: 100 parts of high-density polyethylene, 50 parts of polypropylene, 33.3 parts of linear low-density polyethylene, 53.3 parts of metallocene catalyzed polyethylene, 33.3 parts of thermoplastic polyolefin, 10 parts of free radical initiator, 1.6 parts of antioxidant stabilizer and 6.6 parts of titanium dioxide color master batch.
The density of the high density polyethylene is 0.94g/cm 3 。
The free radical initiator was 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane.
The antioxidant stabilizer is antioxidant 1010.
The method for preparing the base film of the high-density polyethylene waterproofing membrane is the same as that of example 1.
The high-density polyethylene waterproof roll basement membrane with high extensibility obtained in the examples 1-3 and the comparative examples 1-5 is prepared into a high-density polyethylene waterproof roll, and the specific steps are as follows:
after being curled and formed, the high-density polyethylene sheet basement membrane is arranged on a unreeling frame, the sheet is pulled to a gluing mold through pulling tension, a hot melt adhesive layer with a certain thickness is coated according to requirements, and after uniform sanding and sand covering are carried out through a sanding device at the rear section to serve as an isolation layer, the high-density polyethylene waterproof coiled material is finally manufactured through rolling and forming.
The physical and chemical performance tests of the waterproof coiled material are carried out according to the GB/T23457-2017 standard, and the results are shown in the table 1.
TABLE 1 results of Performance test of examples 1-3 and comparative examples 1-3
Comparative example 1 lacks a free radical initiator as compared to the components of the example; comparative example 2 the components of the example lack metallocene-catalyzed polyethylene; comparative example 3 is a conventional high density polyethylene waterproofing membrane base film, lacking the polypropylene, metallocene catalyzed polyethylene, thermoplastic polyolefin, and free radical initiator as compared to the components of the example. The comparative examples were prepared in the same manner as in example 1.
The test result shows that: the tension, tensile strength, elongation at break of the film and nail-bar tear strength of the waterproofing membrane made of comparative example 1 were all significantly lower than those of the examples (also than comparative example 2) because the absence of the radical initiator in the base membrane of the waterproofing membrane of comparative example 1 failed to form a cross-linked network structure and failed to provide high elasticity and high extensibility to the molecular structure.
The puncture resistance of the waterproof roll prepared in the comparative example 2 is obviously lower than that of the embodiment and also lower than that of the comparative example 1, and the metallocene-catalyzed polyethylene can effectively improve the puncture resistance of the bottom film of the high-density polyethylene waterproof roll.
Comparative example 3 is a conventional high density polyethylene waterproofing membrane basement membrane, and all other properties are obviously lower than the examples except that the water impermeability is equivalent to the examples.
Comparative example 4 is a base film of a waterproof roll (based on 100 parts by weight of high density polyethylene) in which the radical initiator was 4 parts by weight, and the high density polyethylene waterproof roll made therefrom was significantly lower in tensile puncture strength and elongation at break of the film than those of examples 1 to 3, and slightly higher than those of conventional high density polyethylene waterproof rolls. It can be seen that the radical initiator can effectively improve the tensile puncture strength and the elongation at break of the high-density polyethylene waterproof roll basement membrane, but when the radical initiator is lower than 6 parts by weight, the elongation of the high-density polyethylene waterproof roll basement membrane is not obviously improved compared with the elongation of the conventional high-density polyethylene waterproof roll basement membrane due to incomplete crosslinking reaction.
Comparative example 5 is a base film of a waterproofing membrane (based on 100 parts by weight of high density polyethylene) in which 10 parts by weight of a radical initiator was used, and the tensile puncture strength and elongation at break of the film of the high density polyethylene waterproofing membrane made therefrom were also significantly lower than those of examples 1 to 3. It can be seen that when the radical initiator is more than 9 parts by weight, the elasticity between the molecular chains is hindered and the elongation is gradually decreased due to the excessively high crosslinking density.
In summary, when 100 parts by weight of high density polyethylene is taken as a reference, the elongation of the high density polyethylene waterproof roll can be effectively improved by controlling the content of the free radical initiator to be 6 to 9 parts by weight.
While the present application has been described with reference to preferred embodiments, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the present application, and in particular, features shown in the various embodiments may be combined in any manner as long as there is no structural conflict. The present application is not intended to be limited to the particular embodiments disclosed herein, but rather to cover all embodiments falling within the scope of the appended claims.
Claims (10)
1. The high-density polyethylene waterproof roll basement membrane is characterized by comprising the following raw material components in parts by weight:
(a) 100 parts by weight of high-density polyethylene;
(b) 40-50 parts of polypropylene;
(c) 30-39 parts by weight of linear low-density polyethylene;
(d) 40-53 parts of metallocene catalyzed polyethylene;
(e) 27-33 parts by weight of a thermoplastic elastomer;
(f) 6-9 parts of a free radical initiator;
wherein the density of the high-density polyethylene is 0.94-0.96 g/cm 3 The density of the metallocene catalyzed polyethylene is 0.92 to 0.94g/cm 3 。
2. The high-density polyethylene waterproof roll bottom film according to claim 1, which is characterized by comprising the following raw material components in parts by weight:
(a) 100 parts by weight of high-density polyethylene;
(b) 40-45 parts of polypropylene;
(c) 30-35 parts by weight of linear low-density polyethylene;
(d) 45-48 parts of metallocene catalyzed polyethylene;
(e) 27-30 parts by weight of a thermoplastic elastomer;
(f) 6-8 parts of a free radical initiator.
3. The base film of high-density polyethylene waterproofing membrane according to claim 1 or 2, wherein the base film further comprises 1 to 2 parts by weight of an antioxidant stabilizer.
4. The high-density polyethylene waterproofing membrane according to claim 1 or 2, further comprising a pigment and a filler.
5. The high-density polyethylene waterproof roll bottom film according to claim 1, which is characterized by comprising the following raw material components in parts by weight:
(a) 100 parts by weight of high-density polyethylene;
(b) 40-45 parts of polypropylene;
(c) 30-35 parts of linear low-density polyethylene;
(d) 45-48 parts of metallocene catalyzed polyethylene;
(e) 27-30 parts by weight of a thermoplastic elastomer;
(f) 6-8 parts of a free radical initiator;
(g) 1.6 to 1.8 weight portions of antioxidant stabilizer;
(h) 6-8 parts of pigment and filler.
6. The carrier film of high density polyethylene waterproofing membrane according to claim 1 or 2, wherein the radical initiator is one or more of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 2, 4-dichlorobenzoyl peroxide, or dicumyl peroxide.
7. The high density polyethylene waterproof roll bottom film according to claim 3, wherein the antioxidant stabilizer is one or more of an antioxidant 1010, an antioxidant 168, an antioxidant B225 or an antioxidant 1330.
8. The high-density polyethylene waterproof coiled material bottom film according to claim 4, wherein the pigment and filler is one or more of titanium dioxide, talcum powder, calcium carbonate, color masterbatch or barium sulfate.
9. The method for preparing the bottom film of the high-density polyethylene waterproof coiled material is characterized by comprising the following steps of:
providing raw material components according to the weight ratio of the high-density polyethylene waterproof coiled material bottom film of any one of claims 1 to 8;
the raw material components are melt mixed to be extruded into a film.
10. A high-density polyethylene waterproof roll characterized by comprising the high-density polyethylene waterproof roll basement membrane according to any one of claims 1 to 8, a hot-melt adhesive layer, and an isolation layer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106285727A (en) * | 2016-03-17 | 2017-01-04 | 中国铁道科学研究院铁道建筑研究所 | Anti-viscous formula splash guard |
| CN106366398A (en) * | 2016-08-27 | 2017-02-01 | 潍坊市宏源防水材料有限公司 | Peroxide cross-linked polyolefin waterproof coiled material and preparation technology thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106285727A (en) * | 2016-03-17 | 2017-01-04 | 中国铁道科学研究院铁道建筑研究所 | Anti-viscous formula splash guard |
| CN106366398A (en) * | 2016-08-27 | 2017-02-01 | 潍坊市宏源防水材料有限公司 | Peroxide cross-linked polyolefin waterproof coiled material and preparation technology thereof |
Non-Patent Citations (1)
| Title |
|---|
| 高密度聚乙烯共混增加薄膜韧性的研究;陈斯佳;《炼油与化工》;20191215(第06期);第17-19页 * |
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